Dipl.-Ing.

Andreas Jrke1

Tutorial Chemical Reaction Engineering:

5. Kinetics I

1Institute

of Process Engineering, G25-217, andreas.joerke@ovgu.de

22-May-14

Tutorial CRE: Kinetics I

Equilibrium: Information about what is possible but no time
eq
information c c t
Kinetics answer the question how fast a reaction reaches its
equilibrium state
kinetics

equilibrium
X eq

equilibrium

kinetics

feasible region

Kinetic information is needed for reactor design and optimization

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Tutorial CRE: Kinetics I

Kinetic description requires knowledge about the reaction rate r
Definition: reaction rate

rvol

1 1 d ni
VR i dt

rmass

1 1 d ni
mcat i dt

1 d ci t
rvol
i dt

For systems with constant volume

(liquid phase reactions)

rvol

1 1 d ni 1 d ci

VR i dt i dt

with ci

ni
VR

Besides this definition there is also a kinetic approach

Depends on the system, catalyst, chemical mechanisms,
Examples: power law, Langmuir-Hinshelwood, Eley-Rideal,
Mars-vanKrevelen, Michaelis-Menten / Monod,

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Tutorial CRE: Kinetics I

In this tutorial: power law for a liquid phase with constant volume
Order of component i (= i for elementary reactions)

rj k j T ci ni

ni = overall order of the reaction

Example: r kT c1A c1.7

overall order of reaction = 2.7
B
Task 5.1: Series reaction (e.q. selective oxidation sequence)
Power law approach
k1
k2
A
B
C

Questions:
Integrated kinetic expression for all three components
cA t 0 cA0 , cB t 0 0, cC t 0 0
Concentration-time curves for different parameter sets
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Tutorial CRE: Kinetics I

Kinetic approach: power law, first order for all reactants

r1 k1cA
r2 k2 cB
Using the approach for the mass balances

R
d ci
i , j rj
dt
j 1

d cA
r1 k1cA

dt

Holds for a batch system

d cB
r1 r2 k1cA k2 cB
dt
with constant volume

d cC
r2 k2 cB

dt

Different solution strategies for the coupled ODE system possible

Linear system!
Laplace Transformation!
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Tutorial CRE: Kinetics I

Laplace transformation

L f t F s f t e st dt
0

i
f t for t 0
1
st
L F s
e F s d s
with s0

2i i
for t 0
0
1

Reduces ODE to AE

AE are easy to solve

Transformations and
inverse transformations
can be found in tables!

ODE
System

hard

Solution
in t

time domain
frequency domain
Algebraic
equations

easy

Solution
in s

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Tutorial CRE: Kinetics I

Laplace tables

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Tutorial CRE: Kinetics I

Some simple rules for LPT

f t F s
d f t
sF s f t 0
dt

cA0
sCB s k1
k 2 CB s
s k1

sCB s c

k1CA s k2CB s

sCC s c

k 2 CB s

0
B

0
C

From (1) follows

cA0
CA s
s k1

k1cA0
CB s
s k1 s k2

Application to our system yields

sCA s cA0 k1CA s

k1cA0
sCC s k2
s k1 s k2

3
*

k1k2 cA0
CC s
s s k1 s k2
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Tutorial CRE: Kinetics I

Inverse transformation generates the time functions!

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Tutorial CRE: Kinetics I

Important transformations from the tables
Solution in time domain

cA t cA0 e k1t
e k1t e k2t
cB t k c

k2 k1
k1t
k2t

k
e

k
e
1
cC t cA0 1 2

2
1

0
1 A

e at

1
s a

e at ebt
1

a b
s a s b
1 be at aebt
1
ab
a b

s s a s b

k1 min 1 0.03
k2 k1 0.1
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Tutorial CRE: Kinetics I

Important transformations from the tables
Solution in time domain

cA t cA0 e k1t
e k1t e k2t
cB t k c

k2 k1
k1t
k2t

k
e

k
e
1
cC t cA0 1 2

2
1

0
1 A

e at

1
s a

e at ebt
1

a b
s a s b
1 be at aebt
1
ab
a b

s s a s b

k1 min 1 0.03
k2 k1 1
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Tutorial CRE: Kinetics I

Important transformations from the tables
Solution in time domain

cA t cA0 e k1t
e k1t e k2t
cB t k c

k2 k1
k1t
k2t

k
e

k
e
1
cC t cA0 1 2

2
1

0
1 A

e at

1
s a

e at ebt
1

a b
s a s b
1 be at aebt
1
ab
a b

s s a s b

k1 min 1 0.03
k2 k1 2
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Tutorial CRE: Kinetics I

Important transformations from the tables
Solution in time domain

cA t cA0 e k1t
e k1t e k2t
cB t k c

k2 k1
k1t
k2t

k
e

k
e
1
cC t cA0 1 2

2
1

0
1 A

e at

1
s a

e at ebt
1

a b
s a s b
1 be at aebt
1
ab
a b

s s a s b

k1 min 1 0.03
k2 k1 10
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Tutorial CRE: Kinetics I

Important transformations from the tables
Solution in time domain

cA t cA0 e k1t
e k1t e k2t
cB t k c

k2 k1
k1t
k2t

k
e

k
e
1
cC t cA0 1 2

2
1

0
1 A

e at

1
s a

e at ebt
1

a b
s a s b
1 be at aebt
1
ab
a b

s s a s b

k1 min 1 0.03
k2 k1 100
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Tutorial CRE: Kinetics I

If an intermediate is consumed very fast

d cA
r1 k1cA
dt
d cB
r1 r2 k1cA k2 cB 0
dt
d cC
r2 k2 cB
dt

Bodenstein steady state

approximation

Simplified solution

cA t cA0 e k1t
cB t

k1cA t
k2

cC t cA0 1 e k1t

k1 min 1 0.03
k2 k1 2

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Tutorial CRE: Kinetics I

If an intermediate is consumed very fast

d cA
r1 k1cA
dt
d cB
r1 r2 k1cA k2 cB 0
dt
d cC
r2 k2 cB
dt

Bodenstein steady state

approximation

Simplified solution

cA t cA0 e k1t
cB t

k1cA t
k2

cC t cA0 1 e k1t

k1 min 1 0.03
k2 k1 5

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Tutorial CRE: Kinetics I

If an intermediate is consumed very fast

d cA
r1 k1cA
dt
d cB
r1 r2 k1cA k2 cB 0
dt
d cC
r2 k2 cB
dt

Bodenstein steady state

approximation

Simplified solution

cA t cA0 e k1t
cB t

k1cA t
k2

cC t cA0 1 e k1t

k1 min 1 0.03
k2 k1 10

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Tutorial CRE: Kinetics I

If an intermediate is consumed very fast

d cA
r1 k1cA
dt
d cB
r1 r2 k1cA k2 cB 0
dt
d cC
r2 k2 cB
dt

Bodenstein steady state

approximation

Simplified solution

cA t cA0 e k1t
cB t

k1cA t
k2

cC t cA0 1 e k1t

k1 min 1 0.03
k2 k1 100

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Tutorial CRE: Kinetics I

Task 5.2: Equilibrium reaction with constant volume

AB

CD

Question:
Derivation of an integrated kinetic expression
Stoichiometric mixture at t = 0

cA t 0 1 mol/l, cB t 0 1 mol/l
cC t 0 0 mol/l, cD t 0 0 mol/l
Using the extend of reaction yields

cA

cB

cC

cD

cA t cB t
cC t cD t cA cA0 cA t

Only description of A is necessary!

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Tutorial CRE: Kinetics I

Power law approach and balance for A

r k cA cB
r k cC cD
2
d cA

0
r r k cA cB k cCcD k cA k cA cA
dt

cA0 cA t
Introducing conversion X A t
cA0
2
2
d cA

0
0 dXA
k cA 1 X A k cA X A cA
dt
dt
dXA
2
0

k cA 1 X A k cA0 X A 2
dt

k cA0 1 2 X A X A 2 X A 2 1
K

k
K
k
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Tutorial CRE: Kinetics I

Continued

dXA
1

k cA0 1 2 X A X A 2 X A 2
dt
K

k cA0 1 2 X A X A 2 1
K

dXA

K 1
k cA0 1 2 X A X A 2

dt
K

Solve ODE with separation of variables Integration

XA

d X A

X A 0

2 K 1

1 2 X A X A K

k cA0

dt

t 0

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Tutorial CRE: Kinetics I

From integration tables (e.g. Bronstein) we find the standard
integral
X

X 0

1
2aX b

ln

2

aX bX c 2aX b 0
d X

with 4ac b 2

Check, if < 0 and evaluate conversion integral

4
4ac b 0
K
2

K 1
X
1
XA

dXA
K
K

ln

2
X K 1 1
X A 0
X 2 K 1
1

2
X

A K
A
A

K K 1
1
K 1

Include this intermediate result in the ODE and integrate over t

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Tutorial CRE: Kinetics I

Continued

K 1
XA
1
K
K 1
XA
1
K

1
K
1
K

2k cA0
K 1
exp
K 1
K

Solve for XA

X A t

2k cA0
t
1 exp
K
K

K 1 K 1
2k cA0
exp
t

K
K 1

cA0 cA t
With the conversion X A t
cA0
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Tutorial CRE: Kinetics I

Continued
The final result

K
0
cA t cA 1
K 1

2k cA0
t
1 exp
K

2k cA0
K 1
exp
t
K 1
K

k / min 1 1

k / min 1 0.1

k / min 1 0.1

k / min 1 1

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